Bis(3-alkoxyalkan-2-ol) sulfides, sulfones, and sulfoxides: new surface active agents

ABSTRACT

Compositions containing surfactant compounds according to formula (I) 
 
ROCH 2 CH(OH)CR 1 R 2 ZCR 1 R 2 CH(OH)CH 2 OR (I), 
 
wherein Z is S, SO, or SO 2 , can have a range of equilibrium and/or dynamic surface tensions and a range of foaming performance attributes, depending upon the particular values of Z, R, R 1 , and R 2 . The compounds of formula (I) may be prepared by a process that includes reaction of a sulfide source such as a metal sulfide or bisulfide with an alkyl glycidyl ether. The compounds may be useful in any of a broad range of applications requiring the use of a surfactant.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of application Ser. No.10/899,419, filed Jul. 26, 2004.

FIELD OF THE INVENTION

This invention relates to surfactant compositions. More particularly, itrelates to adducts of sulfides with glycidyl ethers and their use toreduce the surface tension in water-based systems.

BACKGROUND OF THE INVENTION

The ability to reduce the surface tension of water is of greatimportance in the application of water-based formulations becausedecreased surface tension translates to enhanced substrate wettingduring use. Examples of water-based compositions requiring good wettinginclude coatings, inks, adhesives, fountain solutions for lithographicprinting, cleaning compositions, metalworking fluids, agriculturalformulations, electronics cleaning and semiconductor processingcompositions, personal care products, and formulations for textileprocessing and oilfield applications. Surface tension reduction inwater-based systems is generally achieved through the addition ofsurfactants, resulting in enhanced surface coverage, fewer defects, andmore uniform distribution. Equilibrium surface tension (EST) isimportant when the system is at rest, while dynamic surface tension(DST) provides a measure of the ability of a surfactant to reducesurface tension and provide wetting under high speed applicationconditions.

The importance of the ability of a surfactant to achieve low surfacetension at low use levels, the ability to affect foaming performance,and the surfactant's ability to provide efficient emulsification andsolubilization are all of considerable industrial importance, as iswell-appreciated in the art. And, although equilibrium surface tensionreduction efficiency is important for some applications, otherapplications may require both equilibrium and dynamic surface tensionreduction.

The foaming characteristics of a surfactant are also important becausethey can help define applications for which the surfactant might besuitable. For example, foam can be desirable for applications such asore flotation and cleaning. On the other hand, in coatings, graphic artsand adhesive applications, foam is undesirable because it can complicateapplication and lead to defect formation. Thus foaming characteristicsare frequently an important performance parameter.

The wide variety of applications for which surfactants are used, and theresultant variation in performance requirements, results in a need for acorrespondingly large number of surfactants adapted to these variousperformance demands, and a need for suitable methods for making them.

SUMMARY OF THE INVENTION

In one aspect, the invention provides a formulation including:

-   -   i) a first component consisting of one or more compounds        according to formula (I)        ROCH₂CH(OH)CR, R₂ZCR₁R₂CH(OH)CH₂OR (I)        wherein each R is independently selected from the group        consisting of C4-C20 branched, linear, and cyclic alkyl,        alkenyl, aryl, and aralkyl moieties; C4-C20 branched, linear,        and cyclic alkyl, alkenyl, aryl, and aralkyl moieties bearing a        carbonyl group or one or more heteroatoms selected from O, S,        and N; glycol ether moieties of the formula R₃(OCH₂CH₂)_(n)—;        aminoethylene moieties of the formula R₃(NHCH₂CH₂)_(n)—; and        thioether moieties of the formula R₃S(CH₂)_(n)—; wherein R₃ is H        or linear C1-C12 alkyl and n is an integer from 1 to 15, R₁ and        R₂ are each independently H or a C1-C4 alkyl group, and Z is S,        SO, or SO₂; and    -   ii) a second component consisting of one or more materials        selected from the group consisting of mineral acids, formic        acid, acetic acid, tetramethylammonium hydroxide, nonvolatile        organic materials, nonvolatile inorganic materials, and mixtures        of these, the second component not including any component of a        pre- or post-preparation synthesis reaction mixture for        preparation of any of the one or more compounds according to        formula (I);    -   wherein the formulation is fluid at 25° C.

In another aspect, the invention provides, in a method for drilling,completing, cementing, stimulating, fracturing, acidizing, working over,or treating a subterranean well, an improvement that includes injectinginto the well a fluid including one or more compounds according toformula (I) as defined immediately above.

In yet another aspect, the invention provides, in a method for treatinga produced stream of oil or gas from an oil and gas bearing formation,an improvement that includes injecting into the produced stream a fluidincluding one or more compounds according to formula (I) as definedabove.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel surfactant compositions that arecapable of effectively reducing the dynamic and/or equilibrium surfacetension of aqueous systems, and/or affecting foaming performance of suchsystems. The compositions include bis(3-alkoxyalkan-2-ol) sulfides,sulfones, and sulfoxides according to the following formula (I), whereinZ represents S, SO, or SO₂, respectively:ROCH₂CH(OH)CR₁R₂ZCR₁R₂CH(OH)CH₂OR (I)

Each R is independently a C4-C20 alkyl, alkenyl, aryl, or aralkylmoiety, and may be branched, linear, or cyclic. It may also be such amoiety bearing a carbonyl group, especially a carboxylic acid, ester, oramide, and/or one or more heteroatoms selected from O, S, and N. Suchmoieties may be in any location on R. Typically R is a C8-C18 linearalkyl group, and more typically it is a C12-C16 linear alkyl group. Insome embodiments, R is a C8-C10 or a C12-C16 hydrocarbyl moiety,especially a linear alkyl moiety. R may also be a glycol ether moiety ofthe formula R₃(OCH₂CH₂)_(n)—, an aminoethylene moiety of the formulaR₃(NHCH₂CH₂)_(n)—, or a thioether moiety of the formula R₃S(CH₂)_(n)—,wherein R₃ is H or linear C1-C12 alkyl and n is an integer from 1 to 15.Nonlimiting examples of suitable R groups include butyl, hexyl, octyl,2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, phenyl,cresyl (any isomer, attached at any ring position or at the phenolicoxygen), and mixtures thereof. Typically, the R groups will be one ormore of butyl, 2-ethylhexyl, octyl, decyl, dodecyl, tetradecyl. R₁ andR₂ are each independently H or a C1-C4 alkyl group. Exemplarycompositions according to the present invention are:1,1′-thiobis(3-butoxypropan-2-ol), 1,1′-thiobis(3-octyloxypropan-2-ol),1,1′-thiobis(3-decyloxypropan-2-ol),1,1′-thiobis(3-(2-ethylhexyloxy)propan-2-ol),1,1′-thiobis(3-dodecyloxypropan-2-ol), and1,1′-thiobis(3-tetradecyloxypropan-2-ol).

Preparation of Compounds of Formula (I)

Compounds according to formula (I) may be prepared by any method knownin the synthetic organic chemical art. In one exemplary embodiment ofthe invention, they may be prepared by the reaction of a sulfide sourcewith a glycidyl ether according to formula (II), wherein R, R₁, and R₂are as defined above, and wherein Z=S. Compounds wherein Z is SO or SO₂may be made by oxidation of the corresponding compound where Z is S,using oxidation techniques well known in the art. In one exemplaryembodiment of the invention oxidation is performed with hydrogenperoxide, but other methods may be used.

As used herein, the term “sulfide source” means a composition thatcontains, or otherwise provides, any of hydrogen sulfide, a bisulfideanion, or a sulfide anion. Suitable nonlimiting examples of sulfidesources include compounds M₂S wherein each M is independently selectedfrom the group consisting of H, NH₄, alkali metals, and alkaline earthmetals. Specific examples of suitable sulfides and bisulfides includesodium sulfide, sodium bisulfide, potassium sulfide, potassiumbisulfide, lithium sulfide, and lithium bisulfide in the anhydrous formor as hydrates. Other sulfide sources include alkali metal polysulfidesand disulfides. The amount of glycidyl ether used in the reaction istypically from about 2.0 to about 5 moles per mole of sulfide, moretypically from about 2 to about 3 moles, still more typically from about2 to about 2.5 moles, and most typically about 2 moles per mole ofsulfide. Mixtures of glycidyl ethers may be employed such that thereaction mixture will contain glycidyl ethers having two or moredifferent R groups, two or more different R₁ groups, and/or two or moredifferent R₂ groups. In such a situation, the product may include amixture of compounds according to formula (I) in which some have thesame R, R₁, and R₂ groups on both sides of the molecule, while othershave different embodiments of any or all of these groups on one side vs.the other.

To prepare compounds according to formula (I), the sulfides orbisulfides may be reacted (adducted) with the glycidyl ether, which mayoptionally be dispersed in a reaction medium including a diluent, at atemperature sufficiently high so as to provide a convenient reactionrate and sufficiently low so as to prevent significant by-productformation. By “dispersed,” it is meant that the glycidyl ether issuspended in the medium, dissolved in it, or a combination of these. Thereaction temperature may be in the range from about 50° C. to about 150°C., preferably from about 50° C. to about 130° C., and more preferablyfrom about 60° C. to about 90° C. The optimum conditions will dependupon the specific reactants, the reactor configuration, the solventsemployed, and other variables. A variety of diluents may be used for thereaction, including liquids in which one or more of the reactants isessentially insoluble. More typically, a diluent (if used) will be amaterial that is a solvent for one or more of the reactants. Examples ofsuitable solvents include, but are not limited to, isopropanol, ethanol,methanol, acetonitrile, ethylene glycol, propylene glycol, combinationsof water and acetonitrile, combinations of water and methanol,combinations of water and isopropanol, combinations of water andethanol, and mixtures thereof. Typically, isopropanol will be used.

Uses of Compounds of Formula (I)

Compositions according to the invention may also include a variety ofother ingredients adapted to complement the utility of compounds offormula (I) in a number of applications. The performance properties ofsuch products may be optimized for a specific application by appropriatemodification of the structure of the sulfide and the choice of thesubstituents R, R₁, and R₂. Such optimization is routine, and within theability of the person of ordinary skill in the art in the particularapplication area. Thus manipulation of these variables yields compoundswhich may be useful as emulsifiers or detergents, wetting agents,foaming agents, defoamers, rheology modifiers or associative thickeners,dispersants, and the like. As such, these compounds may be useful inapplications such as coatings, inks, adhesives, agriculturalformulations, fountain solutions, photoresist strippers and developers,shampoos, and detergents and other cleaning compositions. The compoundsmay also find use in oil-field exploration, development, and productionapplications such as enhanced oil recovery, fracturing and stimulationprocesses, and drilling and cementing operations, and may also be usefulin various wet-processing textile operations, such as dyeing of fibersand fiber scouring and kier boiling. The general formulation principlesgoverning each of these applications are well known in the respectivearts, and a detailed description of the numerous application areas andmethods for incorporating the compounds of this invention into suchformulations is not necessary to their effective incorporation therein.However, as an indication of the wide scope of possible uses forcompounds according to the invention, exemplary but nonlimitingformulations are set forth below for a number of application areas.

The terms “water-based”, “waterborne”, “aqueous”, or “aqueous medium”,or “aqueous carrier” as used herein refer to systems in which thesolvent or liquid dispersing medium comprises at least 50 wt % water,preferably at least 90 wt %, and more preferably at least 95 wt % water.The dispersing medium may consist essentially of water, i.e. it may haveno added solvents.

In broad terms, compounds according to formula (I) may be used in a widerange of formulations that include a second component, such that theapplication of the second component benefits from the surface activeproperties provided by the formula (I) material. It is to be understoodthat, although components of a pre- or post-preparation synthesisreaction mixture for preparation of the compounds according to formula(I) may be present, these do not count as part of the second componentfor purposes of this invention. Such materials might for example includesimple salts, solvents, catalysts, organic precursors, reagents, sideproducts, and byproducts related to the preparation of the compound offormula (I). Typically, but not necessarily, the amount by weight of thesecond component in a formulation will be greater than that of thecompound(s) of formula (I).

Formulations containing compounds according to formula (I) according tothe invention are typically constructed so as to be fluid at 25° C. Theyare typically aqueous, but they need not be. The second component mayconsist of one or more materials selected from the group consisting ofmineral acids, formic acid, acetic acid, tetramethylammonium hydroxide,nonvolatile organic materials, nonvolatile inorganic materials, andmixtures of these. As used herein, the term “nonvolatile” means that theindicated material either cannot boil, or it boils at a temperature ofat least 150° C. at a pressure of 760 Torr. Thus, although typicalvolatile solvents may be included in the formulation, they do notconstitute a part of the second component. Such volatile solvents, orwater, or a combination of these, may in some embodiments be part of athird component of the formulation. Typically, the second and thirdcomponents in combination constitute between 0.1 and 99.9 wt % of theformulation.

Typical non-limiting examples of nonvolatile materials are given in theexemplary formulations provided hereinafter. Formulations according tothe invention may include ready-to-use formulations, or concentrates.Either of these may be further diluted in use. Thus the concentration ofthe one or more compounds of formula (I) in a composition according tothe invention may vary over a wide range. Typically it will be between0.001 and 45 wt % of the formulation, although in some cases the amountmay be as low as 0.00001 wt %. In many cases compositions at the higherend of this concentration range will be diluted during or before use inthe intended application, although this is not required in allapplications.

By using compounds of formula (I), it is possible to reduce surfacetension in a waterborne composition or an industrial process. Thus theinvention provides aqueous compositions comprising such compounds,wherein the surfactant provides good wetting properties when used in asurfactant effective amount. For example, the amount of surfactant thatis effective to provide enhanced wetting properties of a water-based,organic compound containing composition may range from 0.00001 to 5 wt%, preferably from 0.0001 to 3 wt %, and most preferably from 0.001 to 3wt %, based on total weight of the formulation. The most favorableamount will vary from one application to another, depending upon theamount and type of other species present in the formulation that arecapable of affecting foam properties and wetting performance, forexample latex polymers.

A typical water-based coating formulation that includes the surfactantsof the invention may include the following components in an aqueousmedium, typically at 30 to 80% solids:

Typical Aqueous-Based Coating Formulation

0 to 50 wt % Pigment Dispersant/Grind Resin 0 to 80 wt % ColoringPigments/Extender Pigments/Anti-Corrosive Pigments/Other Pigment Types 5to 99.9 wt % Water-Borne/Water-Dispersible/Water-Soluble Resins 0 to 30wt % Slip Additives/Antimicrobials/Processing Aids/Defoamers 0 to 50 wt% Coalescing or Other Solvents 0.01 to 10 wt % Surfactant/Wetting/Flowand Leveling Agents, other than Compound of Formula (I) 0.001 to 5 wt %Compound(s) of Formula (I)

A typical water-based ink composition that includes the surfactants ofthe invention may include the following components in an aqueous mediumat a 20 to 60% solids content (i.e. not including the coalescingsolvent):

Typical Aqueous-Based Ink Composition

1-50 wt % Pigment 0 to 50 wt % Pigment Dispersant/Grind Resin 0 to 50 wt% Clay base in appropriate resin solution vehicle 5 to 99.9 wt %Water-borne/water-dispersible/water-soluble resins 0 to 30 wt %Coalescing Solvents 0.01 to 10 wt % Surfactant/Wetting Agents, otherthan Compound(s) of Formula (I)s 0.01 to 10 wt % ProcessingAids/Defoamers/Solubilizing Agents 0.001 to 5 wt % Compound(s) ofFormula (I)

A typical water-based agricultural composition that includes thesurfactants of the invention may include the following components in anaqueous medium at 0.01 to 80% of the following ingredients:

Typical Aqueous-Based Agricultural Composition

0.1-50 wt % Pesticide or Plant Growth Modifying Agent 0.01 to 10 wt %Surfactants, other than Compound(s) of Formula (I)s 0 to 5 wt % Dyes 0to 20 wt % Thickeners/Stabilizers/Co-surfactants/GelInhibitors/Defoamers 0 to 25 wt % Antifreeze agent (e.g. ethylene glycolor propylene glycol) 0.001 to 5 wt % Compound(s) of Formula (I)

A typical fountain solution composition for planographic printing thatincludes the surfactants of the invention may include the followingcomponents:

Typical Fountain Solution for Planographic Printing

0.05 to 10 wt % Film forming, water soluble macromolecule 1 to 25 wt %C2-C12 Alcohol, glycol, or polyol (water soluble, or soluble due to useof a co-solvent) 0.01 to 20 wt % Water soluble organic acid, inorganicacid, or a salt of these 30 to 98.9 wt % Water 0.001 to 5 wt %Compound(s) of Formula (I)

A typical hard surface cleaner that includes the surfactants of theinvention may include the following components:

Typical Hard Surface Cleaner

0 to 25 wt %* Anionic surfactant 0 to 25 wt %* Cationic surfactant 0 to25 wt %* Nonionic surfactant (e.g. alcohol alkoxylates, etc.) 0 to 20 wt% Chelating agent (EDTA, citrate, tartrate, etc.) 0 to 20 wt %* Solvent(Glycol ether, lower alcohols, etc.) 0.001 to 25 wt % Compound(s) ofFormula (I) 0 to 2 wt % Dye, fragrance, preservative, etc. 0 to 40 wt %*Alkali metal hydroxide Balance to 100 wt % Water, and optionally otheringredients*To total, in combination, between 0.1 and 99 wt %.

A typical water-based photoresist developer or electronic cleaningcomposition that includes the surfactants of the invention may includethe following components:

Typical Aqueous-Based Photoresist Developer Composition

0.1 to 3 wt % Tetramethylammonium hydroxide 0 to 4 wt % Phenolic resin92.5 to 99.9 wt % Water 0.001 to 5 wt % Compound(s) of Formula (I)

A typical metalworking fluid that includes the surfactants of theinvention may include the following components:

Typical Synthetic Metalworking Fluid Formulation

2.5 to 10 wt % Block copolymer or other emulsifying agent 10 to 25 wt %Alkanolamine 2 to 10 wt % Organic monoacid 0 to 5 wt % Organic diacid 40to 84.4 wt % Water 1 to 5 wt % Biocide 0.001 to 5 wt % Compound(s) ofFormula (I)

Surfactants are also used in a wide variety of products in the areas ofpersonal care and household and industrial cleaning. The surfactants ofthe present invention may be used in any of these formulations toprovide one or more benefits, with the exact structure of the surfactantcompound depending upon the specific performance features required for aparticular application. Typical formulations used in these markets aredescribed in Louis Ho Tan Tai's book, Formulating Detergents andPersonal Care Products: A Complete Guide to Product Development(Champaign, Ill.: AOCS Press, 2000) as well as in other books,literature, product formularies, etc. familiar to those skilled in theart. A few representative example formulations are described here asillustrations. For example, a rinse aid for use in household automaticdishwashing or in industrial and institutional warewashing may have theingredients described below.

Typical Rinse Aid Formulation

Compound(s) of Formula (I) 0.001 to 45 wt % Nonionic surfactant otherthan a compound 0 to 45 wt % of Formula (I) (e.g. alkoxylatedalcohol(s), alkoxylated block copolymers, etc.) Hydrotrope (e.g. sodiumxylenesulfonate, sodium 0 to 10 wt % toluenesulfonate, anionicsurfactant(s), amphoteric surfactant(s), etc.) Isopropyl alcohol orethyl alcohol 0 to 10 wt % Chelant (e.g. citric acid, etc.) 5 to 20 wt %Water, and optionally other ingredients Balance to 100 wt %

Typical Powdered Laundry Detergent Formulation

Amount by Weight Amount by Weight in Conventional in ConcentratedMaterial Formulation Formulation Compound(s) of Formula (I) 0.001 to 5wt % 0.001 to 15 wt % Detergent surfactant(s) (e.g. 0.1 to 30 wt % 0.1to 50 wt % anionic surfactants, alcohol alkoxylates, etc.)Builder/co-builder (zeolites, 25 to 50 wt % 25 to 60 wt % sodiumcarbonate, phosphates, etc.) Bleach and bleach activator 0 to 25 wt % 0to 25 wt % (perborates, etc.) Other Additives (fragrance, 0 to 7 wt % 1to 10 wt % enzymes, hydrotropes, etc.) Fillers (sodium sulfate, etc.) 5to 35 wt % 0 to 12 wt %

Typical Aqueous Liquid Laundry Detergent Formulation

Amount by Weight Amount by Weight in Conventional in ConcentratedMaterial Formulation Formulation Compound(s) of Formula (I) 0.001 to 25wt % 0.001 to 30 wt % Detergent surfactant(s) (e.g. 0 to 35 wt % 0 to 65wt % anionic surfactants, alcohol alkoxylates, etc.) Builder/co-builder(citrate, 3 to 30 wt % 0 to 36 wt % tartrate, etc.) Other Additives(fragrances, 0.1 to 5 wt % 1 to 5 wt % dyes, etc.) Water and othersolvents 5 to 75 wt % 1 to 56 wt % (e.g. lower alcohols)

Typical Non-Aqueous Laundry Detergent Formulation

Material Amount by Weight Compound(s) of Formula (I) 0.001 to 30 wt %Detergent surfactant(s) (e.g. anionic surfactants, 0.1 to 42 wt %alcohol alkoxylates, amine oxides, etc.) Builder/co-builder (zeolites,sodium carbonate, 25 to 60 wt % phosphates, citrate or tartrate salts,etc.) Bleach and bleach activator (perborates, etc.) 0 to 20 wt %Anti-redeposition aids (sodium 0.5 to 5 wt % carboxymethylcellulose,etc.) Other Additives (fragrance, enzymes, etc.) 0 to 5 wt %Polyalkylene glycol 0 to 50 wt %

Typical 2-Part Industrial and Institutional Laundry Formulation

Amount by Weight of Material in Each Pack Pack A Compound(s) of Formula(I) 0.001 to 20 wt% Detergent surfactant(s) (e.g. anionic surfactants, 0to 20 wt% alcohol alkoxylates, etc.) Antiredeposition aids (sodium 0.01to 2 wt% carboxymethylcellulose, etc.) Water, and optionally otheringredients Balance to 100 wt% Pack B Sodium silicate 5 to 10 wt% Sodiummetasilicate 0 to 30 wt% Tetrapotassium pyrophosphate 0 to 10 wt%potassium hydroxide 0 to 35 wt% potassium carbonate 0 to 15 wt% Water,and optionally other ingredients Balance to 100 wt% Mix Ratio PackA:Pack B 1:2 to 1:4

Typical Shampoo or Liquid Body Wash Formulation

Material Amount by Weight Compound(s) of Formula (I) 0.001 to 5 wt %Anionic surfactant(s) (e.g. sodium or ammonium 0.1 to 30 wt % laurylsulfate, sodium or ammonium lauryl sulfate, etc.) Amphotericcosurfactant(s) (e.g. cocoamidopropyl 0 to 20 wt % betaine, etc.)Nonionic surfactant other than a compound of 0 to 20 wt % Formula (I)(e.g. alcohol alkoxylates, sorbitan esters, alkyl glucosides, etc.)Cationic polymers (e.g. polyquaternium, etc.) 0 to 5 wt % OtherAdditives (fragrance, dyes, oils, opacifiers, 0 to 15 wt %preservatives, chelants, hydrotropes, etc.) Polymeric thickeners (e.g.polyacrylate, etc.) 0 to 2 wt % Conditioning oils (e.g. sunflower oil,petrolatum, 0 to 10 wt % etc.) Citric acid 0 to 2 wt % Ammonium chlorideor sodium chloride 0 to 3 wt % Humectants (e.g. propylene glycol,glycerin, etc.) 0 to 15 wt % Glycol distearate 0 to 5 wt % Cocoamide(i.e. cocoamide MEA, cocoamide 0 to 10 wt % MIPA, PEG-5 cocoamide, etc.)Dimethicone 0 to 5 wt % Behenyl alcohol 0 to 5 wt % Water, andoptionally other ingredients Balance to 100 wt %

Typical Hair Conditioner Formulation

Material Amount by Weight Compound(s) of Formula (I) 0.001 to 10 wt %Nonionic surfactant other than a compound of 0.1 to 10 wt % Formula (I),and/or fatty alcohol(s) (e.g. stearyl alcohol, etc.) Cationicsurfactant(s) (e.g. cetrimonium chloride, 0 to 10 wt % etc.) Anionicsurfactants (e.g. TEA- 0 to 5 wt % dodecylbenzenesulfonate, etc.)Silicones (e.g. dimethicone, dimethiconal, etc.) 0 to 5 wt % Cationicpolymers (e.g. polyquaternium, etc.) 0 to 10 wt % Other Additives(fragrance, dyes, oils, opacifiers, 0 to 10 wt % preservatives,chelants, hydrotropes, etc.) Thickening polymers (e.g.hydroxyethylcellulose, 0 to 5 wt % polyacrylates, etc.) Potassium,ammonium or sodium chloride 0 to 5 wt % Humectant (e.g. propyleneglycol, etc.) 0 to 5 wt % Panthenol 0 to 2 wt % Water, and optionallyother ingredients Balance to 100 wt %

Typical Aqueous Sunscreen Formulation

Material Amount by Weight Compound(s) of Formula (I) 0.001 to 30 wt %Polyethylene glycol (e.g. PEG-8, etc.) 0 to 30 wt % Active sunscreenagents (e.g. octyl 1 to 30 wt % methoxycinnamate, azobenzone,homosalate, octyl salicylate, oxybenzone, octocrylene, butylmethoxydibenzoylmethane, octyl triazone, etc.) Esters and emollients(e.g. dimethicone, 0 to 20 wt % methylparaben, propylparaben,polysorbates, etc.) Thickening polymers (e.g. acrylates/C10-30 alkyl 0to 20 wt % acrylate crosspolymer, PVP/hexadecene copolymer, etc.) OtherAdditives (fragrance, dyes, oils, opacifiers, 0 to 15 wt %preservatives, chelants, etc.) Solvent/hydrotropes (e.g. propyleneglycol, 0 to 20 wt % benzyl alcohol, dicapryl ether, etc.)Triethanolamine 0 to 5 wt % Water, and optionally other ingredientsBalance to 100 wt %

Cement Admixture Formulations

Cement admixtures may be of any of several types, includingsuperplasticizing, plasticizing, accelerating, set retarding, airentraining, water-resisting, corrosion inhibiting, and other types. Suchadmixtures are used to control the workability, settling and endproperties (strength, impermeability, durability and frost/deicing saltresistance, etc.) of cementitious products like concretes, mortars, etc.The admixtures are usually provided as aqueous solutions and they can beadded to the cementitious system at some point during its formulation.Surfactants of this invention may provide wetting, foam control, flowand leveling, water reduction, corrosion inhibition, high ionic strengthtolerance and compatibility, and other benefits when used in suchsystems.

Exemplary Cement Admixture Ingredients

Amount by Weight Relative to Cement Material Weight Compound(s) ofFormula (I) 0.001 to 5 wt % Solubilizing agents (solvent, hydrotropes,amines, 0 to 10 wt % etc.)* Polymers and/or oligomers (e.g.lignosulfonates, 0 to 5 wt % sulfonated melamine formaldehydecondensates, polycarboxylates, styrene-maleic anhydride oligomers,copolymers and their derivatives, etc.)* Functional Additives(defoamers, air entraining or 0 to 5 wt % detraining agents, pH controladditives, corrosion inhibitors, set retarders, accelerators,preservatives, etc.)* Water 40 to 75%*To total, in combination, between 0.1 and 20 wt %.

Oil and Gas Field Formulations

Surfactants of this invention, used alone or as a component informulations, may provide surface tension reduction, foam control, andimproved wetting in a variety of applications within the Oil and Gasindustry. These may include, for example, formulations for the followinguses.

In drilling applications, the surfactants may be used in formulationsfor dispersion of clays and drill cuttings, ROP (rate of penetration)enhancement, emulsification and de-emulsification, surface wetting andsurface tension reduction, shale stabilization, and enhancement ofhydration or dissolution of solid additives.

In cementing, stimulation and workover applications, uses may includeformulations for spacers, cement dispersion, de-air entraining anddefoaming, cement retardation, fracturing fluids, stimulation of coalbed methane, surface or interfacial tension reduction, oil/waterwetting, and cleaning fluids.

In oil and gas production, uses may include rig wash formulations,defoaming of crude, water flooding/injection, defoaming for acid gassweetening, oil/water separation, enhanced oil recovery, and inhibitionor dispersion of asphaltenes, hydrates, scale and waxes.

Exemplary fluids for drilling, completing, cementing, stimulating,fracturing, acidizing, or working over of subterranean wells, or forenhancing production from an oil- or gas-bearing formation or treatingthe produced oil or gas, typically include from 0.05 to 10 wt % of asurfactant of this invention in a fluid containing water and/or anorganic liquid, which typically constitutes from 5 to 99.85 wt % of thefluid. The organic liquid is typically a petroleum product, although itneed not be, and may for example include crude oil or any of thedrilling mud base oils described below. If water is included, it may befrom a freshwater, sea water, or brine source, or it may be provided byinclusion of an aqueous mineral acid such as hydrochloric acid,hydrofluoric acid, sulfuric acid, etc. Fluids for such applicationsusually also include between 0.1 and 80 wt % in total of one or moreingredients selected from weighting agents, viscosifiers, dispersants,drilling mud base oils, emulsifiers, soluble salts, cements, proppants,mineral acids, organic acids, biocides, defoamers, demulsifiers,corrosion inhibitors, friction reducers, gas hydrate inhibitors,hydrogen sulfide removal or control additives, asphaltene controladditives, paraffin control additives, and scale control additives. Avariety of specific materials are known in the art for performing thesefunctions. Suitable nonlimiting examples of some of these materialsfollow, and others will be apparent to those of skill in the art.

-   -   Weighting agents: barium sulfate, hematite, and ilmenite.    -   Viscosifiers: clays (e.g. bentonite, attapulgite), water-soluble        polymers (e.g. xanthan gum, guar, polysaccharides, modified        polysaccharides), organophilic clays, and oil-soluble polymers.    -   Dispersants: lignosulfonates, naphthalene sulfonates, sulfonated        melamine formaldehyde resins.    -   Drilling mud base oils: diesel, mineral oil, olefinic oils,        paraffinic oils, and esters.    -   Emulsifiers: fatty acids, fatty amides, anionic surfactants, and        nonionic alkoxylated surfactants.    -   Soluble salts (e.g. for specific gravity adjustment, shale        stabilization, or osmotic pressure control): NaCl, NaBr, KCl,        KBr, CaCl₂, CaBr₂, ZnCl₂, ZnBr₂, sodium formate, potassium        formate, and cesium formate.    -   Cements    -   Other Surfactants: cationic surfactants, amphoteric surfactants,        alkyl glucosides, phosphate esters, and fluorosurfactants.    -   Proppants: ceramics, sintered bauxite, sand, and resin-coated        sand.    -   Organic Acids: formic acid, acetic acid, citric acid.    -   Mineral acids: hydrochloric acid and hydrofluoric acid.

The foregoing classes of materials may find application, when used incombination with the surfactants of this invention, in a variety ofoilfield applications. Depending upon the exact application and desiredeffect, compositions may be injected into a well or added to the streamof oil or gas produced by the well, all according to methods well knownin the art.

Typical applications, and the ingredients commonly (although notnecessarily) used in making formulations for these purposes, are shownimmediately below. Other ingredients may also be present. It will beunderstood that each of these formulations will also contain asurfactant according to the invention.

-   -   Water-based drilling muds: weighting agents, viscosifiers, and        dispersants.    -   Oil-based drilling muds: base oil, emulsifier, and viscosifier.    -   Completion fluids: soluble salts for specific gravity        adjustment.    -   Cement Formulations: the cements themselves, in combination with        dispersants.    -   Spacers: weighting agents and surfactants.    -   Acidizing fluids: surfactants and one or both of mineral acids        and organic acids.    -   Fracturing fluids: viscosifiers, proppants, and surfactants.

Fluids for stimulating or enhancing production from a gas or oil bearingformation, may contain ingredients similar to those found in fracturingfluids, except for proppants. Finally, fluids for treating oil or gasproduced in the above ways may include one or more of biocides,defoamers, demulsifiers, corrosion inhibitors, friction reducers, gashydrate inhibitors, hydrogen sulfide removal or control additives,asphaltene control additives, paraffin control additives, and scalecontrol additives.

As will be appreciated in light of the foregoing discussion, thesurfactants of this invention may find utility in a wide variety ofapplications. The present invention is further illustrated by thefollowing examples, which are presented for purposes of demonstrating,but not limiting, the methods and compositions of this invention.

EXAMPLES Example 1 Reaction of Sodium Bisulfide with Butyl GlycidylEther

A solution of butyl glycidyl ether (2.91 g, 22.39 mmol) in isopropanol(5 mL) and H₂O (1 mL) was added to sodium bisulfide (0.628 g, 11.20mmol) under nitrogen in a 100 mL 3-neck round bottom flask equipped witha N₂ inlet, a rubber septum, glass stopper and a magnetic stir bar. Themixture was heated at 90° C. and monitored for completion by gaschromatography/mass spectrometry for disappearance of starting materialsand formation of the product. After 3 h, the reaction was judged to becomplete. The mixture was cooled to ambient temperature and treated withsaturated NH₄Cl (5.0 mL) and extracted into ethyl acetate (50 mL). Thesolvent was dried (MgSO₄), filtered, and evaporated in-vacuo to give theproduct, 1,1′-thiobis(3-butoxypropan-2-ol), which was identified by massspectrometry as well as ¹H and ¹³C NMR.

Example 1a Reaction of Sodium Sulfide with Butyl Glycidyl Ether

A reaction was carried out in a manner similar to that described inExample 1, starting from butyl glycidyl ether (2.91 g, 22.39 mmol) andsodium sulfide heptahydrate (2.69 g, 11.2 mmol). The product obtainedwas 1,1,-thiobis(3-butoxypropan-2-ol), identified as in Example 1.

Example 2 Reaction of Sodium Sulfide with Mixture of C12, C14, and C16Glycidyl Ethers

A reaction was carried out in a manner similar to that described inExample 1, starting from sodium sulfide (22.48 g, 288 mmol) and amixture of C12, C14, and C16 glycidyl ethers (139.62 g, ˜576 mmol) in100 mL of isopropanol and 47 mL of H₂O. The product, identified as inExample 1, was a mixture of 1,1,-thiobis(3-dodecyloxypropan-2-ol),1,1,-thiobis(3-tetradecyloxypropan-2-ol),1,1,-thiobis(3-hexadecyloxypropan-2-ol), and three analogous mixedspecies having, respectively, one dodecyloxy and one tetradecyloxygroup, one hexadecyloxy and one tetradecyloxy group, and onehexadecyloxy and one dodecyloxy group.

Example 3 Reaction of Sodium Sulfide with a Mixture of C8 and C10Glycidyl Ethers

A reaction was carried out in a manner similar to that described inExample 1, starting from sodium sulfide (22.48 g, 288 mmol) and amixture of C8 and C10 glycidyl ethers (107.14 g ˜576 mmol), in 100 mL ofisopropanol and 47 mL of H₂O. The product, identified as in Example 1,was a mixture of 1,1,-thiobis(3-octyloxypropan-2-ol),1,1,-thiobis(3-decyloxypropan-2-ol), and the analogous mixed specieshaving one octyloxy and one decyloxy group.

Example 4 Reaction of Sodium Sulfide with 2-Ethylhexyl Glycidyl Ether

A reaction was carried out in a manner similar to that described inExample 1, starting from sodium sulfide (22.48 g, 288 mmol) and2-ethylhexyl glycidyl ether (576 mmol, 107.31 g) in 100 mL ofisopropanol and 47 mL of H₂O. The product obtained was1,1,-thiobis(3-(2-ethylhexyl)oxypropan-2-ol), identified as in Example1.

The reactants and products of Examples 1-4 are shown in Table 1 below.TABLE 1 Sulfide/Glycidyl Ether Adducts Example sulfide Glycidyl EtherProduct 1 Na₂S

SBGE 2 Na₂S

R = mix of R = mix of C₁₂H₂₅, C₁₄H₂₉, C₁₂H₂₅, C₁₄H₂₉, C₁₆H₃₃ C₁₆H₃₃SDDGE 3 Na₂S

R = mix of R = mix of C₈H₁₇, C₁₀H₂₁, C₈H₁₇, C₁₀H₂₁, SOGE 1 Na₂S

SEHGE

Examples 5-8 Equilibrium Surface Tensions

Equilibrium surface tensions were determined for the compounds preparedin Examples 1-4, using a Kruss K-12 tensiometer with a platinum Wilhelmyplate, maintaining the temperature at 25±1° C. by means of a constanttemperature circulating bath. The results, reported in Table 2, areaverages of 10 measurements over a 10-minute period, and have a standarddeviation of less than 0.01 dyne/cm. TABLE 2 Equilibrium Surface TensionData for Sulfide/Glycidyl Ether Adducts Surface Tension Dynes/cm ExampleCompound (0.1 wt %) Solubility 5 SBGE 38.4 <0.1 wt % 6 SOGE 34.0 <0.1 wt% 7 SEHGE 37.9 <0.1 wt % 8 SDDGE 34.2 <0.1 wt %

Examples 9-12 Foam Characteristics of Sulfide/Glycidyl Ether Adducts

Foam height and stability (time to reach zero foam) were measured by theRoss-Miles foam test, using 0.1 wt % solutions of the surfactants. Theresults of these determinations are presented in Table 3. TABLE 3 FoamStability Data Initial Foam Time to 0 foam Example Compound Height (cm)(sec) 9 SBGE 0.7 2 10 SOGE 0 0 11 SEHGE 0 0 12 SDDGE 0 0

The data in Table 3 demonstrate that a range of foam performance may beobtained, depending upon the glycidyl ether capping group. Whileapplications such as coatings, inks, and adhesives require low foam orfoam that dissipates quickly, other applications such as cleaning or orefloatation require a controlled amount of foam to be present and topersist. Therefore, compositions incorporating compounds according toformula (I) may find utility in a wide range of applications.

Examples 13-16 Dynamic Surface Tension Data

Dynamic surface tensions were determined for the compounds prepared inExamples 1-4, at 0.1 and 1.0 wt % levels, using a Kruss BP-2 BubblePressure Tensiometer. The results of these determinations are shown inTable 4. TABLE 4 Dynamic Surface Tension Dynamic surface Dynamic tensionsurface tension (dynes/cm), 0.1 wt % (dynes/cm), 1.0 wt % ExampleCompound 1 b/s 5 b/s 20 b/s 1 b/s 5 b/s 20 b/s 13 SBGE 37 38 38 36 37 3814 SOGE 70 71 71 68 70 71 15 SEHGE 61 68 69 52 57 59 16 SDDGE 72 72 7036 50 52b/s = bubbles/second

The data in Table 4 show that a wide range of dynamic surface tensionreduction is possible with this family of molecules providing differingsurfactants for strong (Example 13) or moderate (Example 16), surfacetension reduction of an aqueous solution or formulation. Depending uponthe mode of application of a formulation and the substrate to be wetted(brush application of an industrial coating, spray application of anindustrial cleaner, roller application of an adhesive), surfactants thatprovide such a wide range of dynamic surface tension reduction may findsignificant commercial utility.

Example 17 Preparation of 1,1′-bis(3-octyloxypropan-2-ol) sulfoxide and1,1′-bis(3-octyloxypropan-2-ol) sulfone

A solution of 1,1-thiobis(3-octyloxypropan-2-ol) (5.0 g, 12.32 mmol) inisopropanol (20 mL) was treated with a 30% solution of H₂O₂ in water(11.2 mL, 98.52 mmol) under nitrogen in a 100 mL 3-neck round bottomflask equipped with an N₂ inlet, a rubber septum, a glass stopper and amagnetic stir bar. The mixture was heated at 60° C. for 24 h. Themixture was cooled to ambient temperature and treated with an aqueoussaturated NaHSO₃ solution (5.0 mL) and extracted into ethyl acetate (50mL). The solvent was dried (MgSO₄), filtered, and evaporated in-vacuo togive the product as a 1:1 mixture of 1,1′-bis(3-octyloxypropan-2-ol)sulfoxide and 1,1′-bis(3-octyloxypropan-2-ol) sulfone, which wereidentified by mass spectrometry as well as ¹H and ¹³C NMR.

This invention provides novel surfactants with properties that makesuitable for use in a wide range of industrial and commercialapplications. Such applications include water-based coatings, inks,adhesives, agricultural formulations, aqueous and non-aqueous cleaningcompositions, personal care applications, and formulations for textileprocessing and oilfield applications.

Although the invention is illustrated and described herein withreference to specific embodiments, it is not intended that the subjoinedclaims be limited to the details shown. Rather, it is expected thatvarious modifications may be made in these details by those skilled inthe art, which modifications may still be within the spirit and scope ofthe claimed subject matter and it is intended that these claims beconstrued accordingly.

1. A formulation comprising: i) a first component consisting of one ormore compounds according to formula (I)ROCH₂CH(OH)CR₁R₂ZCR₁R₂CH(OH)CH₂OR  (I) wherein each R is independentlyselected from the group consisting of C4-C20 branched, linear, andcyclic alkyl, alkenyl, aryl, and aralkyl moieties; C4-C20 branched,linear, and cyclic alkyl, alkenyl, aryl, and aralkyl moieties bearing acarbonyl group or one or more heteroatoms selected from O, S, and N;glycol ether moieties of the formula R₃(OCH₂CH₂)_(n)—; aminoethylenemoieties of the formula R₃(NHCH₂CH₂)_(n)—; and thioether moieties of theformula R₃S(CH₂)_(n)—; wherein R₃ is H or linear C1-C12 alkyl and n isan integer from 1 to 15, R₁ and R₂ are each independently H or a C1-C4alkyl group, and Z is S, SO, or SO₂; and ii) a second componentconsisting of one or more materials selected from the group consistingof mineral acids, formic acid, acetic acid, tetramethylammoniumhydroxide, nonvolatile organic materials, nonvolatile inorganicmaterials, and mixtures of these, said second component not includingany component of a pre- or post-preparation synthesis reaction mixturefor preparation of any of the one or more compounds according to formula(I); wherein the formulation is fluid at 25° C.
 2. The formulation ofclaim 1, wherein the second component is present in a greater amount byweight than the first component.
 3. The formulation of claim 2, theformulation further comprising an aqueous carrier.
 4. The formulation ofclaim 1, wherein Z is S.
 5. The formulation of claim 1, wherein the R isselected from the group consisting of C8-C10 moieties and C12-C16moieties.
 6. The formulation of claim 1, wherein the one or morecompounds of formula (I) constitute between 0.001 and 45 wt % of theformulation and the second component constitutes between 0.1 and 99.9 wt% of the formulation, the second component comprising one or morematerials selected from the group consisting of surfactants and wettingagents other than according to formula (I); solvents; alkali metalhydroxides; water-borne, water-dispersible, or water-soluble resins;flow agents; leveling agents; pigments; processing aids; defoamers;solubilizing agents; pesticides; plant growth modifying agents;water-soluble film-forming macromolecules; water-soluble alcohols,glycols, or polyols; water-soluble acids or salts thereof;tetramethylammonium hydroxide; emulsifying agents; alkanolamines;organic monoacids; biocides; chelants; detergent builders; detergentco-builders; dyes; fragrances; anti-redeposition aids; sunscreen agents;solubilizing agents; polymers; oligomers; functional cement additives;sodium chloride; sodium bromide; calcium chloride; calcium bromide; zincchloride; zinc bromide; cesium formate; hydrochloric acid; hydrofluoricacid; acetic acid; formic acid; and water.
 7. The formulation of claim6, wherein the formulation is a powdered laundry detergent formulationcomprising between 0.1 and 50 wt % of one or more detergent surfactantsand between 25 and 60 wt % of a builder or co-builder, the formulationcomprising between 0.001 and 15 wt % of one or more compounds of formula(I).
 8. The formulation of claim 6, wherein the formulation is anon-aqueous laundry detergent formulation comprising between 0.1 and 42wt % of one or more detergent surfactants, between 25 and 60 wt % of abuilder or co-builder, and between 0.5 and 5 wt % of ananti-redeposition aid, the formulation comprising between 0.001 and 30wt % of one or more compounds of formula (I).
 9. The formulation ofclaim 6, further comprising iii) a third component consisting of one ormore materials selected from the group consisting of volatile organicsolvents and water, wherein the second and third components incombination constitute between 0.1 and 99.9 wt % of the formulation. 10.The formulation of claim 9, wherein the formulation is a hard surfacecleaning formulation comprising water and between 0.1 and 99 wt % intotal of one or more ingredients selected from the group consisting ofanionic surfactants, cationic surfactants, nonionic surfactants otherthan according to formula (I), solvents, and alkali metal hydroxides,the formulation comprising between 0.001 and 25 wt % of one or morecompounds of formula (I).
 11. The formulation of claim 9, wherein theformulation is a coating formulation comprising between 5 and 99.9 wt %of a water-borne, water-dispersible, or water-soluble resin, and between0.01 and 10 wt % in total of one or more other additives selected fromthe group consisting of surfactants, wetting agents, flow agents, andleveling agents, other than according to formula (I), the formulationcomprising between 0.001 and 5 wt % of one or more compounds of formula(I).
 12. The formulation of claim 9, wherein the formulation is an inkformulation comprising between 1 and 50 wt % of a pigment, between 5 and99.9 wt % of a water-borne, water-dispersible, or water-soluble resin,between 0.01 and 10 wt % of a surfactant or wetting agent other thanaccording to formula (I), and between 0.01 and 10 wt % in total of oneor more other additives selected from the group consisting of processingaids, defoamers, and solubilizing agents, the formulation comprisingbetween 0.001 and 5 wt % of one or more compounds of formula (I). 13.The formulation of claim 9, wherein the formulation is an agriculturalformulation comprising between 0.1 and 50 wt % of a pesticide or plantgrowth modifying agent and between 0.01 and 10 wt % of a surfactant orwetting agent other than according to formula (I), the formulationcomprising between 0.001 and 5 wt % of one or more compounds of formula(I).
 14. The formulation of claim 9, wherein the formulation is afountain solution formulation for planographic printing comprisingbetween 0.05 and 10 wt % of a water-soluble, film forming macromolecule,between 1 and 25 wt % of a water-soluble alcohol, glycol, or polyol,between 0.01 and 20 wt % of a water-soluble acid or its salt, andbetween 30 and 98.9 wt % of water, the formulation comprising between0.001 and 5 wt % of one or more compounds of formula (I).
 15. Theformulation of claim 9, wherein the formulation is a photoresistdeveloper formulation comprising between 0.1 and 3 wt % oftetramethylammonium hydroxide and between 92.5 and 99.9 wt % of water,the formulation comprising between 0.001 and 5 wt % of one or morecompounds of formula (I).
 16. The formulation of claim 9, wherein theformulation is a synthetic metalworking fluid formulation comprisingbetween 2.5 and 10 wt % of an emulsifying agent, between 10 and 25 wt %of an alkanolamine, between 2 and 10 wt % of an organic monoacid,between 1 and 5 wt % of a biocide, and between 40 and 84.4 wt % ofwater, the formulation comprising between 0.001 and 5 wt % of one ormore compounds of formula (I).
 17. The formulation of claim 9, whereinthe formulation is a rinse aid formulation comprising water and between5 and 20 wt % of a chelant, the formulation comprising between 0.001 and45 wt % of one or more compounds of formula (I).
 18. The formulation ofclaim 9, wherein the formulation is an aqueous liquid laundry detergentformulation comprising between 0.1 and 65 wt % of one or more detergentsurfactants, between 3 and 36 wt % of a builder or co-builder, between0.1 and wt % in total of one or more other additives selected from thegroup consisting of fragrances and dyes, and between 1 and 75 wt % intotal of one or more other additives selected from the group consistingof water and other solvents, the formulation comprising between 0.001and 30 wt % of one or more compounds of formula (I).
 19. The formulationof claim 9, wherein the formulation is an industrial and institutionallaundry detergent formulation comprising water and between 0.01 and 2 wt% of an anti-redeposition aid, the formulation comprising between 0.001and 20 wt % of one or more compounds of formula (I).
 20. The formulationof claim 9, wherein the formulation is a shampoo or liquid body washformulation comprising water and between 0.1 and 30 wt % of an anionicsurfactant, the formulation comprising between 0.001 and 5 wt % of oneor more compounds of formula (I).
 21. The formulation of claim 9,wherein the formulation is a hair conditioner formulation comprisingwater and between 0.1 and 10 wt % of a nonionic surfactant other thanaccording to formula (I), the formulation comprising between 0.001 and10 wt % of one or more compounds of formula (I).
 22. The formulation ofclaim 9, wherein the formulation is an aqueous sunscreen formulationcomprising water and between 1 and 30 wt % of a sunscreen agent, theformulation comprising between 0.001 and 30 wt % of one or morecompounds of formula (I).
 23. The formulation of claim 9, wherein theformulation is a cement admixture formulation comprising between 40 and75 wt % of water and between 0.1 and 20 wt % in total of one or moresolubilizing agents, polymers, oligomers, or functional additives, theformulation comprising between 0.001 and 5 wt % of one or more compoundsof formula (I).
 24. The formulation of claim 1, wherein the one or morecompounds of formula (I) constitute between 0.05 and 10 wt % of theformulation and the second component constitutes between 0.1 and 80 wt %of the formulation, the second component comprising one or morematerials selected from the group consisting of weighting agents,viscosifiers, dispersants, drilling mud base oils, emulsifiers, solublesalts, cements, proppants, mineral acids, organic acids, biocides,defoamers, demulsifiers, corrosion inhibitors, friction reducers, gashydrate inhibitors, hydrogen sulfide removal or control additives,asphaltene control additives, paraffin control additives, and scalecontrol additives.
 25. The formulation of claim 24, further comprisingbetween 5 and 99.85 wt % in total of at least one of an organic liquidand water.
 26. In a method for drilling, completing, cementing,stimulating, fracturing, acidizing, working over, or treating asubterranean well, the improvement comprising injecting into the well afluid comprising one or more compounds according to formula (I)ROCH₂CH(OH)CR₁R₂ZCR₁R₂CH(OH)CH₂OR  (I) wherein each R is independentlyselected from the group consisting of C4-C20 branched, linear, andcyclic alkyl, alkenyl, aryl, and aralkyl moieties; C4-C20 branched,linear, and cyclic alkyl, alkenyl, aryl, and aralkyl moieties bearing acarbonyl group or one or more heteroatoms selected from O, S, and N;glycol ether moieties of the formula R₃(OCH₂CH₂)_(n)—; aminoethylenemoieties of the formula R₃(NHCH₂CH₂)_(n)—; and thioether moieties of theformula R₃S(CH₂)_(n)—; wherein R₃ is H or linear C1-C12 alkyl and n isan integer from 1 to 15, R₁ and R₂ are each independently H or a C1-C4alkyl group, and Z is S, SO, or SO₂.
 27. In a method for treating aproduced stream of oil or gas from an oil and gas bearing formation, theimprovement comprising injecting into the produced stream a fluidcomprising one or more compounds according to formula (I)ROCH₂CH(OH)CR₁, R₂ZCR₁, R₂CH(OH)CH₂OR  (I) wherein each R isindependently selected from the group consisting of C4-C20 branched,linear, and cyclic alkyl, alkenyl, aryl, and aralkyl moieties; C4-C20branched, linear, and cyclic alkyl, alkenyl, aryl, and aralkyl moietiesbearing a carbonyl group or one or more heteroatoms selected from O, S,and N; glycol ether moieties of the formula R₃(OCH₂CH₂)_(n)—;aminoethylene moieties of the formula R₃(NHCH₂CH₂)_(n)—; and thioethermoieties of the formula R₃S(CH₂)_(n)—; wherein R₃ is H or linear C1-C12alkyl and n is an integer from 1 to 15, R₁ and R₂ are each independentlyH or a C1-C4 alkyl group, and Z is S, SO, or SO₂.